Triazolyl ketones

ABSTRACT

NEW 2 - PHENYL-4-(2&#39;&#39;,4&#39;&#39;-DIHYDROXYBENZOYL)-V-TRIAZOLES AND ETHERS AND ESTERS OF THE 4&#39;&#39;-HYDROXY GROUP THEREOF ARE USED AS PROTECTIVE AGENTS AGAINST LIGHT RAYS FOR LIGHTSENSITIVE ORGANIC MATERIALS. THEY ARE PREPARED BY DEALKYLATING THE CORRESPONDING 2-PHENYL-(2&#39;&#39;,4&#39;&#39;-LOWER-ALKOXYBENZOYL)-V-TRIAZOLES AND REACTING THE COMPOUNDS OBTAINED WITH ALKYLATING AGENTS OR ACYLATING AGENTS.

United States Patent 3,749,732 TRIAZOLYL KETONES Jean Rody and HannsLind, Basel, Switzerland, assignors to Ciba-Geigy Corporation, Ardsley,N.Y.

No Drawing. Filed Mar. 8, 1971, Ser. No. 122,132 Claims priority,application Switzerland, Mar. 11, 1970, 3,601/70 Int. Cl. C07d 55/02 US.Cl. 260-308 A 8 Claims ABSTRACT OF THE DISCLUSURE New 2phenyl-4-(2',4'-dihydroxybenz0yl)-v-triazoles and ethers and esters ofthe 4'-hydroxy group thereof are used as protective agents against lightrays for lightsensitive organic materials. They are prepared bydealkylating the corresponding2-phenyl-(2,4-lower-alkoxybenzoyl)-v-triazoles and reacting thecompounds obtained with alkylating agents or acylating agents.

DETAILED DESCRIPTION The present invention relates to new2-phenyl-4-(2'- hydroxybenzoyl)-v-triazoles (1,2,3-triazoles), toprocesses for their production, and to their use as protective agentsagainst light rays for light-sensitive organic materials, the protectiveagents protecting these materials against the harmful eifect of theUV-rays of light, e.g. where the protective agents form a constituent ofprotective filters against light rays, in that protection is provided bythe material to be protected being covered by film-like structures or byprotective layers which contain these triazole compounds; or to the useof the compounds for the stabilising of light-sensitive organicmaterial, the v-triazole compounds being incorporated into this materialeither homogeneously or on the surface.

Annularly-linked v-triazoles, especially benzotriazoles, have alreadyfrequently been suggested as protective agents against light rays, and,in some cases, have also been put on the market. Compared to this classof substances, the compounds according to the invention have, asprotective agents against light rays, a better fastness to light and, insome fields of application, a better compatibility with the substrateand better fastness to sublimation.

Of the compounds having an isolated triazole ring, 1,2,4-triazoles havealready been suggested as protective agents against light rays. Byvirtue of the inadequate fastness to light of these compounds of thisclass of substances, they are, however, not suitable as stabilisers. Onaccount of their often pronounced acceleration effect on thelight-produced yellowing of the substrates, they have hitherto acquiredno industrial importance.

Furthermore, also v-triazoles with an isolated triazole ring are knownas protective agents against light rays. Surprisingly, it has now beenfound that 2-phenyl-4-(2'- hydroxybenzoyl)-v-triazoles of the followingFormula I have a better protective action, particularly in the longwaveUV-range, a lower volatility, and a better compatibility with thesubstrates than these hitherto known v-triazoles.

The v-triazoles according to the invention correspond to the generalFormula I:

(RI/I)n (Bil/)m In this formula:

R represents hydrogen, alkyl having 1 to 21 carbon atoms, cycloalkylhaving 5 to 10 carbon atoms, alkenyl having 3 to 18 carbon atoms,benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl or alkylphenylhaving 7 to 10 carbon atoms,

R represents hydrogen, alkyl having 1 to 22 carbon atoms, A -alkenylhaving 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbonatoms or alkylcarbonyl having 2 to 18 carbon atoms, and

R" represents alkyl having 1 to 22 carbon atoms, or

chlorine, and

R' represents alkyl having 1 to 22 carbon atoms, chlorine, hydroxyl oralkoxy having 1 to 22 carbon atoms,

n represent 0 to 3,

m represents 0 or 1, whereby n+m shall be 0 to 3.

Alkyl groups designated by R in Formula I are, e.g.: methyl, ethyl,butyl, heptyl, undecyl, pentadecyl or heptadecyl. As the cycloalkylgroup, R represents, e.g. cyclohexyl, cyclopentyl or perhydronaphthyl.As the alkenyl group, R represents, e.g. A or A -propenyl or A-hexadecenyl. If a benzyl group R is substituted by alkyl, this can bemethyl, ethyl, propyl, butyl or tert.- butyl. If R denotes alkylphenyl,it can be, e.g. 4-methylphenyl, ethylphenyl or 4-tert.-butylphenyl.

Alkyl groups denoted by R in Formula I can be, e.g.: methyl, ethyl,propyl, i propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl,hexadecyl, octadecyl or docosyl, whereby these alkyl groups can bebranched or unbranched.

A -alkenyl groups denoted by R are, e.g. A -propenyl,Z-methyl-[M-propenyl] or A -hepdadecenyl. If a benzyl group R issubstituted by alkyl, it can be: methyl, ethyl, propyl, butyl ortert.-butyl. The alkylcarbonyl group can be, e.g.: acetyl, propionyl,Z-ethylhexanoyl, caprylol, lauroyl, palmitoyl or stearoyl.

In Formula I, R" and R can denote identical or different alkyl groupssuch as, e.g. methyl, ethyl, i-propyl, n-butyl, tert.-butyl, n-octyl,1,1,3,3-tetramethylbutyl, dodecyl or octadecyl, and R can be alkoxy suchas, e.g. methoxy, ethoxy, butoxy, octoxy, dodecyloxy, or octadecyloXy.

In compounds of the general Formula I which are particularly suitable asprotective agents against light rays:

R represents hydrogen, alkyl having 1 to 17 carbon atoms, phenyl oralkyl phenyl having 7 to 10 carbon atoms,

R represents hydrogen, alkyl having 1 to 18 carbon atoms, A -alkenylhaving 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbonatoms or alkyl-carbonyl having 2 to 18 carbon atoms, and

The new compounds of Formula I wherein R represents hydrogen can beobtained by dealkylation of compounds of the general Formula II OH H RC- N B;

( ro (RH/)m with 1 equivalent of an alkylating agent or acylating agent.

Mentioned as alkylating agents are: dialkylsulphates such as, e.g.dimethylsulphate or diethylsulphate, l-bromo-, I-chloroalkanes, 2-bromoor 2-chloroal-kanes such as, e.g. l-bromoethane, 1-chloropropane,2-bromopropane, l-bromobutane, 1-bromo-3,3-dimethylpropane, 1-chloro-3,3-dimethylbutane, l-bromohexane, l-bromooctane, l-bromodecane,l-bromododecane, l-bromotetradecane, l-bromohexadecane orl-bromooctadecane, benzyl chloride, 4-tert.-butylbenzyl chloride,alkenylbromides or -chlorides such as, e.g. allyl chloride, allylbromide, methallyl chloride or methallyl bromide.

Mentioned as acylating agents are: acetic anhydride, aliphaticcarboxylic acid chlorides such as, eg propionic acid chloride, valericacid chloride, 2-ethylcaproic acid chloride, caprylic acid chloride,lauric acid chloride, palmitic acid chloride or stearic acid chloride.

The alkylation operations are performed in solvents, such as, e.g.alcohols, ketones or dimethylacetamide, in the presence of acidacceptors such as, e.g. potassium carbonate, potassium hydroxide, orsodium methylate.

The acylation operations are performed under the condition of theSchotten-Baumann reaction. Compounds of Formula II can be produced byconverting a compound of Formula III:

R COOH (III) a Friedel-Crafts reaction, with a compound of Formula IV:

Used as compounds of Formula IV are, e.g.. resorcinolmonomethyl ether,resorcinol-dimethyl ether, resorcinoldiethyl ether, resorcinol-dibutylether, resorcinol-dihexyl ether, resorcinol-dioctyl ether,resorcinol-didodecyl ether. The compounds of Formula III can be obtainedby the following reactions:

(a) The compounds of Formula IIIa:

RHCN

(IIIa) wherein R represents hydrogen, or

(b) The compounds of Formula IIIb R W C-NHz IL i wherein R representsalkyl C1-C17 or phenyl, are subjected to acid or alkalinesaponification, depending on the nature of the substituents R and R',whereby, under correspondingly suitable reaction conditions, O-alkylgroups in the o-position are simultaneously dealkylated in the 2-phenylradical.

The compounds of Formula IIIa are produced, e.g. by reaction ofZ-arylazomalonaldehydeoximes with agents splitting off Water, preferablyacetic anhydride under the Perkin reaction conditions.

The compounds of Formula 1111: are produced, e.g. by the simultaneousreaction of 2-arylazoacylacetic esters with ammonia andcopper-(II)-salts, such as, e.g. copper- (II)-chloride-monohydrate, inalcohol at temperatures of around C. under pressure.

The compounds of the general Formula I wherein R represents hydrogen,alkyl having 1 to 22 carbon atoms, benzyl, alkylbenzyl having 8 to 11carbon atoms, or alkylcarbonyl having 2 to 18 carbon atoms can also beproduced by a Fries rearrangement of a compound of the general formula iR C-O- OR l i I can n/ Depending on the substituents, the v-triazoles ofFormula I according to the invention are, at room temperature andparticularly when in fine dispersion, practically colourless to slightlyyellow solids. They are distinguished by an excellent fastness to light,especially in polymeric carrier substances, and are incorporated intothe sub- 7 strates or into the light-filter base materials in amounts of0.001 to 30 percent by weight, preferably 0.01 to percent by weight,relative to the carrier, whereby this process can produce either purelyphysical mixtures or, Where a reaction occurs with the carrier,chemically modified protective agents against light rays.

Naturally, the v-triazoles according to the invention to be preferred aslight-filters are the ones producing the maximum light absorption.

The main carriers for the compounds of Formula I according to theinvention are organic synthetic materials, i.e. polymeric organiccompounds, that is, thermoplastic and also thermosetting polymers.Thereby suitable are both fully synthetic polymers and natural polymers,as well as polymer-homologous chemical modification products thereof. Ofthe fully synthetic polymers, pure addition polymers and purecondensation polymers are particularly suitable, but also condensationpolymers crosslinked by addition polymerisation.

The addition polymers suitable as carrier materials for the newprotective agents against light rays can be put into the following maintypes:

(1) Homopolymers and copolymers of vinyl and vinylidene monomers whichhave been converted by radical, ionic, or metalorganic polymerisationinitiators into the corresponding polymers. Examples of such monomers,the polymerisates of which are suitable as carrier materials,

are:

Polymerisable ethylenic unsaturated halogenated hydrocarbon compounds,especially vinyl chloride, vinyl fluoride and vinylidene chloride.

Polymerisable hydrocarbons with double-bond capable of addition,especially styrene, isobutylene, ethylene and propylene, whereby boththe atactic and the isotactic polymerisation forms are suitable.

one-Unsaturated polymerisable carboxylic acids and functionalderivatives thereof, such as acrylic acid, methacrylic acid,acrylonitrile, alkyl esters, particularly lower alkyl esters, and amidesof acrylic and methacrylic acid, e.g. the methyl, ethyl, and butylesters of methacrylic acid and acrylic acid.

Polymerisable acyl derivatives of ethylenic unsaturated alcohols andamines, especially those of organic carboxylic acids, whereby aresuitable acyl radicals of alkanoic and alkenoic carboxylic acids havingup to 18 carbon atoms, and of aromatic monocyclic carboxylic acids suchas benzoic acids and phthalic acids, as well as acyl radicals of cycliccarbonic acid imides, such as, e.g. those of cyanuric acid. Examplesare: allyl phthalate, polyallyl melamines, vinyl acetate, vinylstearate, vinyl benzoate and vinyl maleate.

Polymerisable hydrocarbons with conjugated double bonds, such asbutadiene, isoprene, chloroprene.

(2) Homoand copolymers of epoxides, especially of bisepoxides, which areformed by acidor base-catalytic hardening. Suitable in this class, forexample, are polymerisates of bisglycidyl ethers of geminalbis-(p-hydroxyphenyl)-alkanes and -cycloalkanes.

(3) Homoand copolymers of lactams and lactones, particularly thepolymerisates of e-caprolactam.

(4) Homoand copolymers of aldehydes, especially of formaldehyde andacetaldehyde, such as polyoxymethylene and polyoxyethylene.

(5) Addition products of isocyanates with hydroxyl and/or aminocompounds, particularly such ones of dior polyisocyanates with biorpolyvalent hydroxyl or amino compounds. This class embraces thepolyurethanes and polyureas which are formed by reaction ofdiisocyanates with polyesters and/or polyethers containing hydroxylgroups.

The condensation polymers suitable as carrier materials for thev-triazoles according to the invention are, among others, especiallypolyesters and polyamides. To be mentioned thereby are, in particular,linear thermoplastic polycondensates which, on the one hand, are derivedfrom dicarboxylic acids and organic dihydroxy derivatives or organicdiamines, and, on the other hand, from hydroxyor aminocarboxylic acids.Preferred linear polycondensates are the fibre-forming polymers ofw,w-dicarboxylic acids and w,w-dihydroxy compounds, or w,w'-diamines, aswell as those of whydroxycarboxylic acids or of w-aminocarboxylic acids,particularly such polymers derived from saturated aliphatic,cycloaliphatic and carbocyclic non-annularly-linked aromatic carboxylicacids.

Especially suitable are the linear condensation products of thefollowing components: adipic acid hexamethylenediamine, sebacic acidhexamethylenediamine, terephthalic acid ethylene glycol, terephthalicacid-1,4-dimethylol-cycloh'exane, IO-aminodecanecarboxylic acid,(l'l-aminoundecyclic acid).

C.oss-linked polycondensates as carrier materials are thermosetting andare formed, in particular, by condensation of aldehydes with polyvalentcompounds capable of condensation. Mention is made for formaldehydecondensates with phenols, ureas and melamines.

Of the condensation polymers cross-linked by subsequent additionpolymerisation, those to be mentioned, in particular, are the polyesterresins, i.e. copolymerisates of polyesters of unsaturated organiccarboxylic acids, which contain double bonds capable of addition, withpolyvalent, especially bivalent alcohols, whereby, optionally, thesepolyesters are modified, on the one hand, with dicarboxylic acids notcapable of addition, and, on the other hand, with vinyl orvinylidenemonomers. Suitable monomers are preferably olymerisablemixtures of condensates of maleic acid, itaconic acid, citraconic acidwith bivalent alcohols, preferably the water-addition-products ofethyleneand propylene oxide, such as ethylene glycol, propylene glycoland diethylene glycol and, optionally, further dicarboxylic acids of thealiphatic-alicyclic and monocyclic-aromatic series, or their anhydridessuch as succinic acid anhydride, phthalic acid anhydride, and/or adipicacid, and of styrene and/or methyl methacrylate. This monomer mixture ofthe unsaturated polyesters and vinyland/or vinylidenemonomers (oftencalled liquid polyester resin) is preferably cross-linked by radicalpolymerisation initiators.

The natural polymers which are suitable as carrier materials for the 2phenyl-4-(2'-hydroxybenzoyl)-v-triazoles according to the invention are,in particular, polysaccharides such as cellulose, or also rubber andproteins.

Of the polymerhomologously chemically modified synthetic polymers,mention is made, in particular, of the reaction products of polyvinylalcohols with aldehydes such as polyvinylbutyral, and of thesaponification products of polyvinyl esters. Polymerhomologouslychemically modified natural polymers as carrier materials for the newprotective agents against light rays are, in particular, celluloseesters and cellulose ethers, such as cellulose esters of acetic acid,propionic acid, benzoic acid, having, on average, 1 to 3 acyl groups perglucose unit.

The polymers listed in the foregoing constitute in the compositionsaccording to the invention, the polymers being either on their own or inadmixtures, the carriers of the new protective agents against lightrays. Particularly valuable compositions according to the inventioncontain, as carriers of the new protective agents against light rays,cellulose esters, polyester resins, polymethacrylic acid esters,polyvinyl chloride, polyethylene and polypropylene.

Also suitable as carrier materials for the new protective agents againstlight rays are, in addition to the above mentioned polymeric carriers,natural as well as synthetic light-sensitve waxes, fats and oils, andalso complex systems such as photographic material, emulsions containinglight-sensitive fatty substances, emulsions or dispersions of theaforementioned polymers.

The molecular weight of the aforestated polymers is of secondaryimportance, as long as it within the limits necessary for thecharacteristic mechanical properties of the respective polymers.Depending on the polymers, it can be 1,000 to several millions. Incorporation of 2-phenyl-4-(2'-hydroxylbenzoyl)-v-triazoles into thesepolymers is effected, for example, depending on the nature of thepolymers, by at least one of these compounds and, optionally, furtheradditives such as, e.g. softeners, antioxidants, other protective agentsagainst light rays, heatstabilisers, and pigments, being worked into themelt by methods usual in engineering, either before or after moulding,or by dissolving in the corresponding monomer before polymerisation, orby dissolving of the polymer and additives in solvents which aresubsequently evaporated oif.

The new protective agents against light rays may also be applied frombaths, e.g. from aqueous dispersions, or from solution in organicsolvents, to polymer granulateand to thinner carrier structures, such asto films or threads.

Further additives are, e.g. antioxidants such as pheno compounds, forexample:

2,2-thiobis-(4-methy1-6-tert.butylphenol)4,4'-thiobis-(3-methyl-6-tert.butylphenol) 2,2-methylene-bis-4-methyl-6-tert.butylphenol);2,2-methylene-bis(4-ethyl-6-tert.butylphenol) 4,4'-methy1ene-bis-(2-methyl-6-tert.butylphenol)4,4-butylidene-bis-(3-n1ethyl-6-tert.butylphenol) 2,2-methylene-bis-[4methyl-6- (a-methylcyclohexyl) phenol]; 2,6-di-2-hydroxy-3-tert.butyl-5-methylbenzyl -4-methylphenol;1,1,3-tris-(4-hydroxy-2-methyl-5-tert.butylphenyl)- butane;1,3,5-trimethy1-2,4,6-tri-(3,5-di-terLbutyl-4-hydroxybenZyD-benZene;esters of 5 4 hydroxy-3,5-di-tert.butylphenylpropionlc acid with monoorpolyvalent alcohol such as methan01, octadecanol, hexanediol,trimethylolethane or pentaerythrite; 2,4-bis-octylmercapto-6(4hydroxy-3,S-di-terLbutylamlino -s-triazine;2,4-bis-(4-hydroxy-3,5-ditert.butylphenoxy)-6-octylmercapto-s-triazine,1, 1-bis-(4-hydr0xy-2-methy1-5-tert.butylphenyl) -3-dodecylmercaptobutane; 4-hydroxy-3,S-di-terLbutylbenzylphosphonic acidester, such as diethyl or dioctadecyl ester;(3-methyl-4-hydroxy-5-tert.butylbenzyl) -malonic ac1d dioctadecyl ester;s- 3,5 -dimethyl-4-hydroxybenzyl -thioglycol1c acid octadecyl ester;

(b) Amine derivatives, for example:

phenyl-l-naphthylamine;

phenyl-Z-naphthylamine;

N,N-diphenyl-p-phenylenediamine;

N,N-di-Z-naphthyl-p-phenylenediamine;

N,N'-di-sec.butyl-p-phenylenediamine;

6-ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline;

6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline;

monoand dioctyliminodibenzyl;

polymerised 2,2,4-trimethyl-1,2-dihydroquinoline, UV-absorbers andprotective agents against light rays, such as:

(a) 2-(2-hydroxyphenyl)-benzotriazoles, e.g. the 5- rnethyl-,3',5-ditert.butyl-, 5'tert.-butyl-, 5-chloro-3'-, 5- ditert.butyl,5-chloro-3-tert.butyl-5'-methyl-, 3',5'-ditert. amyl-,3-rnethyl-5-fi-carbornethoxyethyl-, 5-chloro-3,5'-ditert.amyl-derivative;

(b) 2,4-bis-(2'-hydroxyphenyl)-6-a1kyl-s-triazines, for example, the6-ethy1- or 6-undecyl-derivative;

(c) Z-hydroxybenzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy-, 4-decy1oxy-, 4-dodecyloxy-, 4,2,4-tri-hydroxyor2-hydroxy-4,4-dimethoxy-derivative;

(d) Aryl esters of optionally substituted benzoic acids such as, forexample, phenylsalicylate; octylphenylsalicylate; benzoylresorcinol;3,5di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert.-butyl-phenyl ester;dibenzoylresorcinol;

(e) Acrylates, for example, a-cyano-fi,fi-diphenylacrylic acid ethylorisooctyl-ester; a-carbomethoxycinnamic acid methyl ester; a-cyano-3-methyl-p-methoxycinnamic acid methylor butyl-ester;N-(dcarbomethoxywinyl)-2- methylindoline;

(f) Nickel compounds, for example, nickel complexes of2,2'-thiobis-(4-di-tert.octylphenol), such as the 1:1 and 2:1 complex,optionally with other ligands such as nbutylamine;nickeldibutyldithiocarbamate; nickel salts of4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters suchas methyl-, ethylor butyl-ester, the nickel complex of2-hydroxy-4-methylacetophenoneoxime;

(g) Oxalic acid diamides, e.g., 4,4'-di-octyloxyanilide;2,2-di-octyloxy-5,5'-di-tert.butyloxanilide; 2,2di-dodecyloxy-5,5-di-tert.butyloxanilide; metal-deactivators such asmonoand dihydrazides of monoand polybasic acids such as oxalic, adipic,salicylic, terephthalic or isophthalic acid; substituted oxamides andoxanilides; N-salicyloylsalicylaldehyde-hydrazone; n-butylbenzotriazole;tetrahydrobenzotriazole; 2-guanidinobenzimidazole, nucleation agentssuch as 4-tert.butylbenzoic acid, adipic acid, diphenylacetic acid;peroxide-decomposing compounds such as esters of B-thiodipropionic acid,e.g. the lauryl, stearyl, myrystyl or tridecyl ester; salts ofZ-mercaptobenzimidazoles, e.g. zinc salt; diphenylthiourea; phosphitessuch as triphenylphosphite; diphenylalkylphosphites;phenyldialkylphosphites; trinonylphenylphosphite; trilaurylphosphite;trioctadecylphosphite; 3,9-diisodecyloxy-2,4,8,10- tetraoxa 3,9diphosphaspiro-(5,5)-undecane;tri-(4-hydroxy-3,5-di-tert.butylphenyl)-phosphite.

Other stabilisers such as potassium, barium, cadmium, magnesium, calciumor zinc salts of organic acids, e.g. stearates or laurates; basic orneutral lead salts of organic or inorganic acids; tin-containingstabilisers such as dibutyl tin laurates, -maleates or -n1arcaptides;hexamethylphosphoric acid triamide; copper salts such as copper acetatesor copper-I- or copper-lI-halides, optionally in combination with alkalihalides, -hypophosphites, -phosphites and -phosphates or freephosphorous acids or phosphoric acid; manganese-I-I-salts, such as thechloride, hypophosphite or phosphate, optionally in combination withother hydrophosphites, phosphites and phosphates; dicyandiamide;diphenylurea.

Other additions such as softeners, antistatics, flameproofing agents,pigments, soot.

Inorganic fillers, e.g. asbestos, glass fibres, kaolin, talcum.

The light-sensitive materials can be protected from the harmful actionof light also by them being coated with a protective layer, e.g. with alacquer, containing at least one 2-phenyl-4-(2'-hydroxybenzoyl)-v-triazole according to the invention; or by them being covered withstructures containing such protective agents against light rays, e.g.structures such as films, discs or plates. In these two cases, theamount of added protective agent against light rays is advantageously1030% (relative to the protective layer material) for protective layersof less than 0.01 mm. thickness and for protective layers of 0.0l0.1 mm.thickness.

In the case of certain modes of application, especially where hot chipsof polymer substances are being powdered with protective substances,products are particularly valuable which melt above the softeningtemperature of the polymers concerned and which, nevertheless, aresutficiently soluble in the molten polymer.

The following examples illustrate the invention; the temperatures in theexamples are given in degrees centigrade.

1 1 EXAMPLE 1 Production of 2-phenyl-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole An amount of 106 g. of2-phenylazomalonaldehydeoxime, produced according to DRP 9'47468 (1956),is added in portions, over a period of 30 minutes, to 400 ml. of aceticanhydride heated to 60", whereby the temperature of the reaction mixturegradually rises to 70, the resulting exothermic reaction being completedafter 1 hour. The mixture is then fully reacted over a period of 6 hoursat the reflux temperature. After removal by evaporation in vacuo ofexcess acetic anhydride and formed acetic acid, the brown-colouredresidue is recrystallised, with the aid of active charcoal, fromalcohol/water. In this manner is obtained 2 phenyl-4-cyano-1,2,3-(2H)-triazole in the form of colourless crystals, M.P. 94-95 An amount of 85g. of 2-phenyl-4-cyano-1,2,3-(2H)- triazole is refluxed in a mixture of300 ml. of glacial acetic acid and 400 ml. of hydrobromic acid (48%) for12 hours, and the crystallisate, obtained after cooling to roomtemperature, washed with water and dried. Recrystallisation fromchlorobenzene, with the use of bleaching earth, yields2-phenyl-4-carboxy-1,2,3-(2H)-triazole in the form of colourlesscrystals, M.P. 187-189".

An amount of 94.5 g. of 2-phenyl 4 carboxy-1,2,3- (2H)-triazole issuspended in 200 ml. of chlorobenzene; to the suspension are added 200ml. of thionyl chloride, and the whole is heated to 80 until theevolution of gas has ceased. After cooling to room temperature,concentration by evaporation to dryness is carried out, and thecrystalline residue recrystallised from ligroin. By this means isobtained 2-phenyl-4-chlorocarbonyl-1,2,3-(2H)- triazole, M.P. 112, inform of colourless crystals.

An amount of 107 g. of 2-phenyl-4-chlorocarbonyl- 1,2,3-(2H)-triazole isidssolved in 1,000 ml. of 1,1,2,2- tetrachloroethane; to this solutionare then added in portions at temperatures of below 10, whilst stirringis proceeding, 138.2 g. of powdered aluminium chloride. To the reactionsolution are then added dropwise at -10, within 30 minutes, 69 g. ofrecorcindimethyl ether, and the internal temperature is subsequentlyslowly raised to 55, whereby the cleavage of hydrochloric acidcommences. The reaction is completed at about 60. The colour of thereaction solution hereby gradually changes to reddish-yellow. Aftercooling to room temperature, the reaction solution is hydrolysed withice/hydrochloric acid, and the solvent removed by steam distillation.After washing with water and drying of the crude product,recrystallisation from glacial acetic acid is carried out and 2-phenyl-4-(2-hydroxy 4 methoxybenzoyl)-1,2,3-(2H)- triazole, M.P.173-175, obtained as yellowish crystals; -max. 343 i mol-ar 5 If,instead of 2-phenylazomalonaldehydeoxime, equimolar amounts of2-(4-n-butylphenyl)-azomalonaldehydeoxime,2-(2-methoxyphenyl)-azomalonaldehydeoxime, or 2-(2,5-dichlorophenyl)-azomalonaldehydeoxime are used, the procedure beingotherwise as described above, then by way of the following4-carboxytriazoles 1.1-1.3 are obtained, as intermediate products, theprotective agents against light rays 1.4-1.6.

1.1 2-(4-n-butylphenyl)-4-carboxy-1,2,3-(2H)-triazole,

1.2 2- (2-hydroxyphenyl -4-carboxy- 1,2,3- (2H triazole, M.P. 198-199";

1.3 2-(2,5-dichlorophenyl)-4-carboxy-1,2,3-(2H)- triazloe, M.P. 190-192;

1.42-(4-n-butylphenyl)-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole,M.P. '94-95, Amax. 342 l, moIar 16,000;

1.52-(2-hydroxyphenyl)-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole,M.P. 146-147, A 346 l" molar i 12 1.6 2- (2,5-dichlorophenyl -4-2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole, M.P. 173174, A 343 l:molar EXAMPLE 2 Production of 2-phenyl-4- (2,4-dihydroxybenzoyl) -1,2,3-

(2H) -triazole An amount of 28.1 g. of2-phenyl-4-(2-hydroxy-4-methoxybenzoyl) 1,2,3 (2H)-triazole (Example 1)is suspended in 300 ml. of benzene; to the suspension are added, withstirring, 40 g. of powdered aluminium chloride, the whole is heated toreflux temperature, and this temperature maintained for 2 hours. Aftercooling to room temperature, hydrolysis is performed withice/hydrochloric acid, the solvent removed by steam distillation, thefine-grained yellow reaction product washed with water, dried, andrecrystallised from chlorobenzene. In this manner is obtained2-phenyl-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole, M.P. 154155, inthe form of yellow crystals, k 338 III/1., 6 14,900.

If, instead of2-phenyl-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole, equimolaramounts of the compounds stated in Example 1 under 1.4-1.6 are used,with the procedure otherwise as described above, then the protectiveagents against light rays 2.1-2.3 are obtained.

2.1 2- (4-n-butylphenyl) -4- (2,4-dihydroxybenzoyl 1,2,3-(2H)-triazole,M.P. 118119, k 333 my, molar 2.2 2- 2-hydroxyphenyl -4-(2,4-dihydroxybenzoyl 1,2,3(2H)-triazole, M.P. 187-188", A 333 mu, s14,300;

2.3 2-(2,5-dichlorophenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole, M.P. 200-201, A 333 m e 12,200.

EXAMPLE 3 Production of 2-phenyl-4-(2-hydroxy-4-noctyloxybenzoyl) -1,2,3- 2H -triazole An amount of 25.6 g. of2-phenyl-4-(2,4-dihydroxybenzoyl)-l,2,3-(2H)-triazole is dissolved in200 ml. of methanol; to this solution are then added 5 g. of sodiummethylate, the solution is concentrated by evaporation, and the residuedissolved in 300 ml. of dimethylacetamide. Whilst stirring ismaintained, 18.4 g. of l-bromooctane are then added dropwise at 2040and, after the addition is completed, the reaction mixture is held for 4hours at After cooling to room temperature, the reaction product isprecipitated by the careful addition of dilute acetic acid. Afterwashing with water, and recrystallisation from acetonitrile is obtained2-phenyl-4- (2-hydroxy-4-n-octoxybenzoyl)-1,2,3-(2H)-triazole in theform of slightly yellowish-coloured crystals, M.P. 8283, max. 343 imolar 14,600-

If, instead of l-bromooctane, equivalent amounts of the below statedhalogen compounds are used, then the protective agents against lightrays given under 3.1-3.7 are obtained. For 3.1, 3.2 and 3.5 is used2-(4-n-butylphenyl)-4-(2,4-dihydroxybenzoyl) 1,2,3 (2H)-triazole(Example 2.1), for 3.4 is used 2-(2-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl) 1,2,3 (2H)-triazole (Example 2.2), and for 3.7 isused 2-(2,5-dichlorophenyl)-4-(2,4- dihydroxybenzoyl)-1,2,3-(2H)triazole, the procedure being in each case as described above.l-chloro-Z-methylpropene- (2 1-chloro-3-methylbutane, l-bromodecane, 1bromotetradecane, 1 bromooctadecane, 4 tert.butylbenzyl chloride.

3 .1 2- 4-n-butylphenyl) -4-{2-hydroxy-4- [2-methyl- (2)]-oxybenzoyl}1,2,3-(2H)-triazole, M.P. 107-108, x 342 III/1., e 16,400;

3 .2 2- (4-n-butylphenyl -4- 2-hydroxy-4-3-methylbutyl)-oxybenzoyl]-1,2,3-(2H)-triazole, M.P. 93-94", k 342 me, e16,700;

3.3 2-phenyl-4-(2-hydroxy-4-decyloxybenzoyl)-1,2,3-

( 2H) -triazo1e, M.P. 83-84", Amax. 343 m 6 14,500;

3.42-(2-hydroxyphenyl)-4-(2-hydroxy-4-tetradecyloxybenzoyl)-1,2,3-(2H)-triazole,M.P. 98-100", a 347 mu, emohr 17,800;

3.5 2-(4-n-butylphenyl)-4-(2-hydroxy-4-octadecyloxy-'benzoyl)-1,2,3-(2H)-triazole, M.P. 74-75", a 340 m e 16,400;

3 .6 2-phenyl-4- [2-hydroxy-4- (4-tert.butylbenzyl) oxybenzoyl] 1,2,3-(2H -triazole, M.P. 85-87", k 312 m emolar 15,500;

3.7 2-(2,5-dichlorophenyl)-4-(2-hydroxy-4-octadecyloxybenzoyl 1 ,2,3-(2H -triazole, M.P. 76-78", A 342 lTl/L, 6 12,100.

EXAMPLE 4 Production of 2-(4-n-butylphenyl)-4-('2-hydroxy-4-propionyloxybenzoyl)-1,2, 3- 2H) -triazole To a solution of 16.9 g. of2-(4-n-butylphenyl)-4-(2,4- dihydroxybenzoyl)-1,2,3-(2H)-triazole(Example 2.1) and 3.96 g. of pyridine in 75 ml. of dioxane are addeddropwise within 10 minutes, at temperatures below 15 4.63 g. ofpropionic acid chloride in 10 ml. of dioxane. The reaction is completedin 2 hours at room temperature, and the solution is subsequently heatedfor a further 10 minutes to 80. It is then cooled to room temperatureand the oil, precipitating as a result of the addition of water, istaken up in methylene chloride; the organic phase is washed successivelywith 2-n hydrochloric acid and with water, dried over sodium sulphate,and the solvent evaporated 01f. By crystallisation of the residue fromnhexane is obtained 2-(4-n-butylphenyl)-4-(2-hydroxy-4-propionyloxybenzoyl)-1,2,3 (2H) triazole as yellowish crystals, M.P.128-129"; 1 342 mp, emolar 13,900.

If, instead of2-(4-n-butylphenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole,equimolar amounts are used of2-(2-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl)- 1,2,3-(2H)-triazole(Example 2.2), or 2-phenyl-4-(2,4- dihydroxybenzoyl) 5 methyl 1,2,3 (2H)triazole (Example 6,7), and this reacted, according to the abovedirections, with stearic acid chloride or acetyl chloride, then thefollowing protective agents against light rays are obtained:

4.12-(Z-hydroxyphenyl)-4-(2-hydroxy-4-stearoyloxybenzoyl)-1,2,3-(2H)-triazole,M.P. 95-96", k 343 m 6 13,400;

4.2 2-phenyl-4-(2-hydroxy-4-acetoxybenzoyl)-5-methy1-l,2,3-(2H)-triazole, M.P. 130-131", A 337 m E 11,600.

EXAMPLE 5 Production of 2-(S-rnethoxyphenyl)-4-(2-hydroxy-4-dodecyloxybenzoyl) 1,2,3- (2H) -triazole An amount of 473 g. of2-(3-methoxyphenyl)-azomalonaldehydeoxime is reacted in 1,000 ml. ofacetic acid anhydride, analogously to Example 1. After distillation inhigh vacuum is obtained, as yellowish oil solidifying in the receiver,2-(3-methoxyphenyl)-4-cyano 1,2,3-(2H)- triazole, B.P. 148-151/1.2 torr.

An amount of 283 g. of 2-(3-methoxyphenyl)-4-cyano- 1,2,3-(2H)-triazoleis dissolved in 800 ml. of ethylene glycol monomethyl ether; to thissolution are added 430 g. of a 30% aqueous sodium hydroxide solution,and the whole is refluxed until the evolution of ammonia has ceased. Thereaction solution is then acidified, whilst being cooled with ice, with2-n hydrochloric acid, and the crude 2-(S-methoxyphenyl)-4carboxy 1,2,3(2H) triazole dried after being Washed with water. Recrystallisationfrom toluene yields colourless crystals, M.P. 149-151".

An amount of 265 g. of 2-(3-methoxyphenyl)-4-carboxy-1,2,3-(2H)-triazoleis reacted with 250 ml. of thionyl chloride, analogously to Example 1,to give 2-(3-methoxy- 14 phenyl)-4-chlorocarbonyl 1,2,3 (2H) triazole.Recrystallisation from ligroin, with the aid of bleaching earth, yieldscolourless crystals, M.P. 75-76".

An amount of 23.8 g. of2-(3-methoxyphenyl)-4-chlorocarbonyl-1,2,3-(2H)-triazole is dissolved in50 ml. of 1, 1,2,2-tetrachloroethane; to this solution are then added inportions, at temperatures below 10, 26.6 g. of powdered aluminiumchloride. To the reaction mixture are subsequently added dropwise at10", within 15 minutes, 44.7 g. of resorcinoldidodecyl ether in 30 ml.of 1,1,2,2-tetrachloroethane, and the internal temperature is thereupongradually raised to 60", whereby the generation of hydrochloric acidoccurs. The reaction is completed at this temperature; as the reactionproceeds, the colour of the reaction solution changes to reddish-brown.After cooling to room temperature, hydrolysis with ice-hydrochloric acidis performed, and the solvent expelled by steam distillation. Afterwashing of the oily residue with water and crystallisation from acetone,crude 2-(3-methoxyphenyl)- 4-(2-hydroxy 4 dodecyloxybenzoyl) 1,2,3 (2H)-triazole is obtained, which, after chromatography on silica gel [75-325mesh, eluting agent benzene/hexane 1:9] is in the form of slightlyyellowish crystals melting at 79- max. 342 i molar If, instead ofresorcinoldidodecyl ether, equivalent amounts of resorcinoldimethylether, resorcinoldipropyl ether and resorcinoldihexyl ether are used,then the protective agents against light rays 5.1-5.3 are obtained.Instead of 2-(3-methoxyphenyl) azomalonaldehydeoxime is reacted for5.2:Z-phenylazomalonaldehydeoxime, and in the case of5.3:2-(4-n-butylphenyl)azomalonaldehydeoxime, the procedure in bothcases being as described above.

EXAMPLE 6 Production of 2-phenyl-4- (2-hydroxy-4-methoxybenzoyl)-S-methyl-1,2,3-(2H)-triazole In a pressure vessel are heated, for 10hours at 150 g. of 2-phenylazoacetoacetic ester, g. of copper-(II)-acetate-monohydrate and 130 g. of ammonia gas in 2,000 ml. ofalcohol. After cooling of the reaction solution to room temperature,hydrogen sulphide gas is passed through the solution until the completeprecipitation of copper sulphide has occurred; the solution issubsequently treated with active charcoal in the boiling heat, andfiltered off. The solvent in the filtrate is evaporated oil", and theresidue repeatedly recrystallised from alcohol. Thus obtained is2-phenyl-4-carbonamido-S-methyl-1,2,3- (2H)-triazole, M.P. 175-176", inthe form of colourless crystals.

An amount of 86 g. of 2-phenyl-4-carbonamido-5-metl1-yl-1,2,3-(2H)-triazole is refluxed in 400 ml. of a 1:1-mixture ofglacial acetic acid and hydrobromic acid (48%) for 10 hours. Aftercooling to room temperature, the crude 2-phenyl-4-carboxy 5 methyl 1,2,3(2H) triazole is precipitated by addition of water, and recrystallisedfrom alcohol. Colourless crystals are obtained, M.P. 200-201.

An amount of 65 g. of 2-phenyl-4-carboxy-S-methyl- 1,2,3-(2H)-triazoleis suspended in ml. of toluene; to the suspension are added 200 g. ofthioyl chloride, and refluxing is performed until the generation of H 01has finished. After the reaction solution has been evaporated oil todryness, the residue is crystallised from ligroin,

whereby is obtained 2-phenyl-4-chlorocarbonyl-S-methyl-1,2,3-(2H)-triazole, M.P. 110-111, in the form of colourless crystals.

58 g. of 2-phenyl-4-chlorocarbonyl methyl-1,2,3- (2H)-triazole, 70 g. ofpowdered aluminium chloride and 36.2 g. of resorcinoldimethyl ether arereacted in 400 ml. of 1,1,2,2-tetrachloroethane, as described inExample 1. After recrystallisation from toluene is obtained 2-phenyl-4-(2-hydroxy 4 methoxybenzoyl) 5 methyl 1,2,3- (2H)-triazole, M.P.145-146, in the form of slightly yellow coloured crystals, Amax' 342 me,E 15,260.

If, instead of Z-phenylazoacetoacetic ester, equimolar amounts of2-(Z-methoxyphenyl)-azoacetoacetic ester, 2-(Z-methoxyphenyl)-azostearoylacetic ester and 2-phenylazobenzoylaceticester are used, with the procedure otherwise as described above, then byWay of the following 4-carboxytriazoles 6.1-6.3 are obtained, asintermediate products, the protective agents against light rays 6.4-6.6.

phenyl-1,2,3-(2H)triazole, M.P. 132-133, k 337 mu, s 14,400.

The protective agents against light rays given under 6.7 and 6.9 wereobtained by demethylation of 6, 6.4 or 6.6, corresponding to the data inExample 2.

6.7 2 phenyl-4-(2,4-dihydroxybenzoyl)-5-methyl-1,2,3-

(2'H)-triazole, M.P. 197198, k 335 my, 5 14,200;

2 (2-hydroxyphenyl)-4- (2,4-dihydroxybenzoyl)-5- methyl1,2,3-(2H)-triazole, M.P. 180-181", k 338 mp, emolar 14,700;

2 phenyl-4-(2,4-dihydroxybenzoyl)-5-phenyl-1,2,3- (2H)-triazole, M.P.205-206, A 335 m f l 16,300.

EXAMPLE 7 Production of2-phenyl-4-(2-hydroxy-4-dodecyloxybcnzoyl)-5-methy1-1,2,3-(2H)-triazole10 g. of 2-phenyl-4-(2,4-dihydroxybenzoyl)-5-methyl- 1,2,3-(2H)-triazole(Example 6.7) are dissolved, together with 8.5 g. of l-brornododecaneand 4.7 g. of potassium carbonate, in 150 ml. of dimethylacetamide, andthe solution is allowed to stand for 4 hours at 110. After cooling toroom temperature, the reaction solution is acidified with dilutehydrochloric acid; the reaction product is then precipitated with water,Washed, and recrystallised from acetonitrile. In this manner is obtained2-phenyl-4-(2-hydroxy 4 dodecyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole,M.P. IDS-109, as slightly yellow coloured crystals; A 342 m E 16,280.

If, instead of l-bromododecane, the equivalent amount of the belowlisted alkyl bromides are used, then the protective agents against lightrays given under 7.1- 7.5 are obtained. Instead of2-phenyl-4-(2,4-dihydroxybenzoyl)-5-methyl-1,2,3-(2H)-triazole isreacted for 7.2: (Example 6.8), for 7.4 and 7.5:2-phenyl4-(2,4-dihydroxybenzoyl)-5-phenyl-1,2,3-(2H)-triazole, thereaction being performed as specified: l-bromoethane, l-bromooctane,l-bromohexadecane, l-brornooctadecane.

7.1 2phenyl-4-(2-hydroxy-4-octyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole,M.P. 94-95, k 342 mu, molar 16,100;

EXAMPLE 8 A solution of 15 g. of acetyl cellulose having on average 2.5acetoxy groups per glucose unit, and 0.075 g. of one of the UV-absorberslisted in the following table in g. of acetone is spread out on a glassplate to form a film. The cellulose acetate films obtained afterevaporation of the acetone are dried firstly at room temperature, andthen in an oven at 60. Specimens of these 0.04 mm.-thick UV-filters areexposed, for measurement of the fastness to light of the UV-absorbers,for 500 hours in a Fade-O- Meter, and then examined with respect totheir residual UV-absorption. The obtained results are given in thefollowing table.

erised, after the addition of 0.25% by Weight of a UV- absorbed from thetable below, with 1% by weight of benzoyl peroxide at a temperature of80, to form 2.5 mm. thick sheets. The sheets are subsequently thermosetat Sheets thus produced and then exposed exhibit appreciably lessbrowning than identically exposed sheets not containing the aforestatedUV-absorbers.

The applied polyester resin was produced as follows: To a mixture of g.of ethylene glycol and 292 g. of diethylene glycol is added in portions,at 80, a mixture of 343 g. of maleic acid anhydride and 428 g. oftetrachlorophthalic acid anhydride. After the air has been expelled inthe reaction vessel by nitrogen, the temperature is raised in the courseof 1 hour to 150", then in the course of 9 hours to 210, and thistemperature is maintained for a further hour. The mass is afterwardscooled to 180, vacuum is applied, and the pressure slowly reduced to 100torr. These conditions are maintained until the acid number of thereaction mixture has sunk to below 50.

An amount of 100 g. of the thus obtained polyester is mixed with 50 g.of styrene, and the mixture is polymcriscd under the above describedconditions.

Similar results are obtained if, instead of tetrachlorophthalic acid,the equivalent amount of phthalic acid anhydride is used. In this case,however, the resulting polyester resin is not difiicultly combustible.

If, in the above process, the styrene is replaced by methylmethacrylate,then sheets are obtained which actually exhibit less inclination tobrown and which, more over, are more easily stabilised.

Percent Transmission Transloss at 440 mission nm. after at 440 nm. 1,000hours of before Fade-O-Meter No. UV-Absorber exposure exposure None 8925 2.2..-- 2-(2-hydroxyphenyl)-4-(2,4-dihy- 82.5

droxybenzoyl)-l,2,3-(2H)-triazloe). 6.7-..- 2-phenyl-4-(2,4dihydroxybenzoyl)- 84.5 0.5

-methyl-1,2,3-(2H)-triazole. 6.8..-.2-(2rhydroxyphenyl)-4-(2,4-dihydrox- 84.5 0

ybenzoyl)-5-methyl-1,2,3-(2H)- triazole. 2.3..-.2-(2,5-dichlorphenyl)-4-(Z,4-dihydrox- 86 1.5

ybenzoyl)-1,2,3-(2H)-triazole. 6.0-.-- 2phenyl-4-(2-hydroxy-4-methox- 861.5

ybenzoyl)-5-methyl-1,2,3-(2H)- triazole. 1.5....2-(2-hydroxyphenyl)-4-(2-hydroxy- 84 1.0

4-methoxybenzoyl)-1,2,3-(2H)- triazole. 1.0----2-phenyl-4-(2-hydroxy-4-methoxy- 86.5 2.0

benzoyl)-l,2,3-(2H)-triazole. 2.1...-2-(4-n-butylphenyl)-4-(2,4-dihydrox- 86 1.5

ybenzoyl)'1,2,3-(2H)-triazole. 1.4.--.2-(4-n-buty1phenyl)-4-(2-hydroxy4- 86 2.0

meilzhoxybenzoyl)-1,2,3-(2H)-tri- 9.20 e. 3.1....2-(4-n-bntylphenyD-4-l2hydroxy 84.5 0.5

4-[2-methylpropenyl-(2)]oxybenzoyl }-1,2,3(2H)'triazole. 3.2.-.-2-(4-n-butylphonyl)4-[2-hydroxy-4- 85.5 1.5

(ii-methylbutyl)-oxybenzoyl]- 1,2,3-(2H)-triazole.

Percent trans mission of light of wave-length No. UV-absorber 340 nm.430 nm.

7.2-.-. 2-(2-hydroxyphenyl)4-(2-hydroxy-4 2 92hexadeeyloxybenzoyl)-5-methyl-1,2,3- (2H)-triazole. 3.7.-.-2-(2,5-dichlorphenyl)-4-(2-hydroxy-4- 2 92octadecyloxybenzoyl)-1,2,3-(2H)triazole.

EXAMPLE 100 parts of methacrylic acid methyl ester, 0.5 part of aUV-absorber from the following table, and 0.2 part of lauroyl peroxideare mixed, and then polymerised at a temperature of 50-70 to form sheetsof 2 mm. thickness.

As can be seen from the following table, such sheets can be used asUV-filters.

tetradecyloxybenzoyl)1,2,3-(2H)- triazole.

EXAMPLE 1 1 Processed on a two-roller-mill in the usual manner into theform of sheet is a mixture of:

100 parts of a suspension polyvinyl chloride (K-value 60), 2.5 parts ofa dialkyl tin mercaptide stabiliser 18 (ADVASTAB 17M of the DeutschenAdvance Produktion GmbH, Germany,

1.0 part of an epoxy stabiliser (ADVABLAST 39 of the aforestated firm),

1.0 part of a wax used as lubricating and processing agent (Wax E of thefirm Farbwerke Hoechst, Germany), and

0.2 part of a UV-absorber from the following table.

Specimens of these sheets are exposed for 2,000 hours in the XenotestExposure Apparatus, and then examined for discolouration. The resultsare given in the following table.

Appearance of the exposed No. UV-absorber specimens None Dark-browndiscoloration of the whole specimen. 1.5..-- 2-(2-hydroxyphenyD-4-(2-Somewhat yellowish.

hydroxy-4 methoxybenzoyl)- 3.1.... 2-(4-n-butylphenyl)4-(2-hydroxy-4-[2-methylpropenyl- (2)1-oxybenzoyl)-1,2,3-(2H)- triazole.

3.0.... 2-phenyl-4-(2-hydroxy4-n- Isolated yellowish-brownish areas.

Yellowlng commencing at gctyltixybenzoyl)-1-2-3-(2H)- isolated points.

riazo e. 7.0...- 2-phenyl-4(2-hydroxy-4-d0de- Slightly yellowish.

6.5..-. 2-(2-hydr0xyphenyD-4-(2- hydroxy-a-methoxybenzoyb-6-heptadecy1-1,2,3-(2H)- triazole.

Yellowish at isolated points.

If, instead of the aforementioned mixture, the following recipe is used:

parts of suspension polyvinyl chloride (K-value 62),

1.2 parts of a barium-cadmium-soap (MARK WS of SA.

Argus Chemical N.V., Belgium),

0.5 part of an organic phosphite (MARK C of the aforementioned firm),

1.0 part of a wax (Wax) E of Farbwerke Hoechst, Germany) and 0.2 part ofa UV-absorber from the following table, the procedure being otherwisethe same, then the results given in this table are obtained.

Isolated yellow discolore. butylbenzyl)oxybenzoyl]- tions. 1,2,3-(2H)-triazole.

3.7-..- 2(2,5-diehlorphenyl)-4-(2- Somewhat yellowish.

hydroxyA-octadecyloxybenzoyl)-1,2,3-(2H)-triazole.

EXAMPLE 12 100 parts of polyethylene having a density of 0.917 arehomogeneously mixed at 180 in a Brabender-plastograph with 0.5 parts ofa UV-absorber from. the following table, and

0.5 parts of .3-(3',5-di-t.buty.l-4-hydroxyphenyl)-propionic acidoctadecyl ester.

The thus obtained mass is pressed in a platen press at to form 1 mm.thick sheets.

After weathering, these sheets exhibit, on being bent around 90",appreciably less tendency to be brittle than sheets without the additionof the additives in the table below.

N0. UV-absorber 1.4...-2-(4-n-biitylphenyl)4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)- triazo e.7.4..-. 2-pheny1l-4-(2-hydroxy-4-athyloxybenzoy1)-5-pheny1-1,2,3-(2H)-az e.

3.3.... 2-phenyl-4-(2-hydroxy-4-deeyloxybenzoyl)-1,2,3-(2H)-triazole.

5.0...- 2-(3-methoxyphenyl)-4-(2-hydroxy-4-dodecyloxybenzoly)4,2,3-

(2H)-triazole.

3.4.-.- 2-(2-hydroxyphenyD-4-(2-hydroxy-4tetradecyloxybenzoyl)-1,2,3-(2H)-triazole.

7.2-... 2-(2-hydroxyphenyl)-4(2-hydroxy-ihexadeeyloxybenzoyl)--methyl-1,2 3-(2H)-tn'azole.

3.7-... 2-(2,5-dichlorphenyl)-4-(2-hydroxy-4-octadecyloxybenzoyl)4,2,3-

EXAMPLE 13 After weathering, these sheets exhibit, on being bent around90, appreciably less tendency to be brittle than sheets producedotherwise identically, but without the addition of the protective agentsagainst light rays contained in the following table.

No. UY-absorber 1.4...-2(iin-btitylphenyl)-4-(2-hydr0xy-4-methoxybenzoyl)-1,2,3-(2H)- riazo e.7.4.... 2-rt1geny11-4-(2-hydroxy--ethoxybenzoyl)-5-pheny1-1,2,3-(2H)-azo e.

tnazole. 7.1-...2-lghenyll-4-(Z-hydroxy-et-octyloxybenzoyl)-5-methyl-l,2,3-(2H)- zo e na3.3.... 2-phenyl-4-(2-hydroxy-4-decyloxybenzoyl)-1,2,3-(2H)-triazole.5.0.... 2-(3-methoxyphenyl)4-(2-hydroxy-4-dodeeyloxybenzoyl)4,2,3-

(2H)-triazo1e. 3.4.... 2-2-h3y (l2roxyphen3ll)-4-(2-hydroxyi-tetradecyloxybenzoyl)- ,2, -tr1az 7.2-... 2-(2hydroxypheny1)-4-(2-hydroxy-4-hexadecyloxybenzoyD- S-methyl-LZ3-(2H)-triazole. 3.7.... 2-(2,5-d1chlorpenyl)-4-(2-hydroxy-4-octadecyloxybenzoyl)- 1,2,3-(2H)-triazole.

EXAMPLE 14 Bleached maple-veneer is coated with a wood-lacquer of thefollowing composition:

15.0 parts by weight of cellulose acetate (of the firm Bayer inLeverkusen, Germany) having a ca. 56% acetic acid content,

10.0 parts by weight of dimethyl glycol phthalate,

1.0 part by weight of2-phenyl-4-(2-hydroxy-4-dodecyloxybenzoyl-5-methyl-l,2,3-(2H)-triazo1e(Example 7),

5.0 parts by weight of methyl alcohol,

10.0 parts by weight of toluene, and

50.0 parts by weight of ethyl acetate.

The natural yellowing of the Wood is prevented by this lacquer.

20 EXAMPLE 1s A cosmetic preparation protecting against light rays isobtained as follows:

5 parts of white ceresin wax,

22 parts of white petrolatum,

19.5 parts of white mineral oil,

15 parts of lanolin, free from water,

2 parts of2-(4-n-butylphenyl)-4-(2-hydroxy-4-hexyloxybenzoyl)-1,2,3-(2H)-triazole(Example 5.3),

36 parts of water,

0.5 part of perfume.

The ceresin, petrolatum and lanolin are melted together and theprotective agent against light rays dissolved in the melt. The mineraloil is thereupon added at 70, and subsequently the water slowly workedin at the same temperature. Stirring is continued until the temperaturehas fallen to below 50, whereupon the perfume is added.

EXAMPLE 16 A sprayable cosmetic protective agent against light rays isobtained by dissolving in parts of ethanol,

10 parts of ricinic acid methyl ester,

10 parts of oleyl alcohol, and

1 part of2-(4-n-butylphenyl)-4-(2-hydroxy-4-hexyloxybenzoyl)-1,2,3-(2H)-triazole(Example 5.3).

After addition of the usual commercial fluorine-containing propellants(e.g. Freon-products of the firm Du Pont, U.S.A.), the solution can besprayed from an aerosol container.

We claim:

1. Compounds of the general Formula I:

wherein:

R represents hydrogen, alkyl having 1 to 21 carbon atoms, cycloalkylhaving 5 to 10 carbon atoms, alkenyl having 3 to 18 carbon atoms,benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl or alkylphenylhaving 7 to 10 carbon atoms,

R represents hydrogen, alkyl having 1 to 22 carbon atoms, A -alkenylhaving 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbonatoms or alkylcarbonyl having 2 to 18 carbon atoms, and

R" represents alkyl having 1 to 22 carbon atoms, or

chlorine,

R represents the same as R", hydroxyl or alkoxy having 1 to 22 carbonatoms,

22 represents 0 to 3,

m. represents 0 or 1,

n=+m1 represents 0 to 3.

2. Compounds according to claim 1 of the general Formula I wherein:

R represents hydrogen, alkyl having 1 to 17 carbon atoms,

phenyl or alkylphenyl having 7 to 10 carbon atoms,

R represents hydrogen, alkyl having 1 to 18 carbon atoms,

A -alkenyl having 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to11 carbon atoms, or alkylcarbonyl having 2 to 18 carbon atoms, and

R" represents alkyl having 1 to 18 carbon atoms, or

chlorine,

21 R'" represents the same as R", hydroxyl or alkoxy having 1 to 8carbon atoms, and n represents 0 to 3, m represents 0 or 1, and n+mrepresents 0 to 3.

3. Compounds according to claim 1 of the general Formula I wherein:

R represents hydrogen, alkyl having 1 to 17 carbon atoms, or phenyl,

R represents hydrogen, alkyl having 1 to 18 carbon HZOIIIS, A -alkenylhaving 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbonatoms, or alkylcarbonyl having 3 to 18 carbon atoms, and

R" represents butyl or chlorine,

R' represents the same as R", hydroxyl or alkoxy,

n represents 0 to 2,

m represents 0 or 1, and

n+m represents 0 to 2.

4. 2-pheny1-4-(2-hydroxy 4 dodecyloxybenzoyl) 5-methyl-1,2,3-(2H)-triaz01.

5. 2-phenyl-4(2,4-dihydroxybenzoy1)-5-methy1 1,2,3- (ZH) -triazo1.

6. 2-(Z-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl) 5-methyl-1,2,3-(2H)-triazol.

7. 2-(2-hydroxypheny1)-4-(2-hydroxy- 4methoxybenzoyl)-5-methy1-1,2,3-(2H)-triazo1.

8. 2-pheny1-4-(2-hydroxy-4-n-octy1oxybenzoyl) 1,2,3- (2H)-triazo1.

References Cited UNITED STATES PATENTS US. Cl. X.R.

